EP1537183A1 - Beschichtungsmasse zur herstellung einer isolierfolie, deren verwendung zur herstellung einer isolierfolie, daraus hergestellte isolierfolie für halbleitervorrichtung sowie selbige enthaltende halbleitervorrichtung - Google Patents

Beschichtungsmasse zur herstellung einer isolierfolie, deren verwendung zur herstellung einer isolierfolie, daraus hergestellte isolierfolie für halbleitervorrichtung sowie selbige enthaltende halbleitervorrichtung

Info

Publication number
EP1537183A1
EP1537183A1 EP04724894A EP04724894A EP1537183A1 EP 1537183 A1 EP1537183 A1 EP 1537183A1 EP 04724894 A EP04724894 A EP 04724894A EP 04724894 A EP04724894 A EP 04724894A EP 1537183 A1 EP1537183 A1 EP 1537183A1
Authority
EP
European Patent Office
Prior art keywords
branched
linear
fluorine
insulating film
organic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP04724894A
Other languages
English (en)
French (fr)
Other versions
EP1537183B1 (de
EP1537183A4 (de
Inventor
Myung-Sun Moon
Min-Jin Ko
Hye-Yeong Nam
Jung-Won Kang
Bum-Gyu Choi
Byung-Ro Kim
Gwi-Gwon Kang
Young-Duk Kim
Sang-Min Park
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
LG Chem Ltd
Original Assignee
LG Chem Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by LG Chem Ltd filed Critical LG Chem Ltd
Publication of EP1537183A1 publication Critical patent/EP1537183A1/de
Publication of EP1537183A4 publication Critical patent/EP1537183A4/de
Application granted granted Critical
Publication of EP1537183B1 publication Critical patent/EP1537183B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04Polysiloxanes
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/14Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which at least two but not all the silicon atoms are connected by linkages other than oxygen atoms
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02107Forming insulating materials on a substrate
    • H01L21/02109Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02112Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
    • H01L21/02123Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
    • H01L21/02126Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material containing Si, O, and at least one of H, N, C, F, or other non-metal elements, e.g. SiOC, SiOC:H or SiONC
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02107Forming insulating materials on a substrate
    • H01L21/02109Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02205Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition
    • H01L21/02208Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si
    • H01L21/02214Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and oxygen
    • H01L21/02216Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being characterised by the precursor material for deposition the precursor containing a compound comprising Si the compound comprising silicon and oxygen the compound being a molecule comprising at least one silicon-oxygen bond and the compound having hydrogen or an organic group attached to the silicon or oxygen, e.g. a siloxane
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02107Forming insulating materials on a substrate
    • H01L21/02225Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
    • H01L21/0226Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process
    • H01L21/02282Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a deposition process liquid deposition, e.g. spin-coating, sol-gel techniques, spray coating
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/312Organic layers, e.g. photoresist
    • H01L21/3121Layers comprising organo-silicon compounds
    • H01L21/3122Layers comprising organo-silicon compounds layers comprising polysiloxane compounds
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104Forming layers
    • H01L21/02107Forming insulating materials on a substrate
    • H01L21/02109Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
    • H01L21/02203Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates the layer being porous
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31652Of asbestos
    • Y10T428/31663As siloxane, silicone or silane

Definitions

  • the present invention relates to a coating composition for insulating film
  • SiO 2 having a dielectric constant of 4.0 is primarily used.
  • SiO 2 having a dielectric constant of 4.0 is primarily used.
  • fluorine-doped silicate F-SiO 2
  • F-SiO 2 fluorine-doped silicate
  • F-SiO 2 becomes thermally unstable as the fluorine content
  • organic polymers have dielectric constants ranging from 3.2 to 2.6.
  • Organic silicate polymers are prepared by hydrolyzing alkoxy
  • silane compounds in organic solvents and condensing the same.
  • polyhydrosilsesquioxane have relatively low dielectric constants of 3.0 or lower, and are thermally stable at 450 TJ . However, polysilsesquioxane may crack
  • insulating materials have dielectric constants of 2.7 or higher, and it is a
  • Patent Publication No. 2001-354903 Japanese Patent Publication No. 2001-354903
  • a coating composition for insulating film production comprising an
  • organic silicate polymer prepared using an acid catalyst and an organic silicate
  • the dielectric constant may increase abruptly.
  • the base because the base
  • a salt may be produced, which may cause generation of impurities during long-term storage.
  • FIG. 1 is a graph showing the molar ratio of the hydroxy group of organic
  • the present invention provides a coating
  • composition for insulating film production comprising: a) an organic polysiloxane
  • the present invention also provides a preparation method of a low
  • dielectric insulating film comprising the steps of: a) preparing an organic compound
  • polysiloxane precursor having a weight-average molecular weight ranging from
  • the present invention also provides a low dielectric insulating film for a semiconductor device which is prepared by the above-mentioned method and
  • R 1 is hydrogen, an aryl, a vinyl, an allyl, or a linear or branched C ⁇ to C
  • R 2 is a linear or branched C ⁇ to C 4 alkoxy
  • p is an integer of 1 or 2.
  • each of R 3 and R 5 is hydrogen, fluorine, an aryl, a vinyl, an allyl, or a
  • each of R 4 and R 6 is a linear or branched Ci to C 4 alkoxy
  • M is a Ci to C 6 alkylene or phenylene
  • each of q and r is an integer of 0 to 2.
  • R 7 is hydrogen, fluorine, an aryl, a vinyl, an allyl, or a linear or branched
  • Ci to C alkyl substituted by fluorine or unsubstituted
  • R 8 is hydrogen, a hydroxy, or a linear or branched Ci to C 4 alkoxy or
  • R 9 is fluorine, an aryl, a vinyl, an allyl, or a linear or branched Ci to C 4
  • R 10 is a linear or branched Ci to C 4 alkoxy
  • each of m and n is an integer of 3 to 7.
  • the present invention also provides a semiconductor device comprising
  • the present invention provides a coating composition for insulating film
  • the present inventors worked for a composition for insulating film
  • compositions comprising no water or a trace of water while having low
  • a low dielectric insulating film for a semiconductor device is prepared by
  • coating a coating composition for insulating film production comprising an
  • silanol groups of the organic polysiloxane are condensed to form
  • the coating composition for insulating film production of the present invention is a coating composition for insulating film production of the present invention.
  • invention comprises an organic polysiloxane precursor having a weight-average
  • molecular weight ranging from 500 to 30,000, an organic solvent, and water.
  • the organic polysiloxane precursor preferably has a weight-average molecular
  • weight ranging from 500 to 30,000, more preferably from 500 to 10,000.
  • organic polysiloxane precursor having a smaller molecular weight prevents pore
  • the organic polysiloxane precursor has 80% or more and
  • the silane compound used to prepare the organic compound preferably, the silane compound used to prepare the organic compound
  • polysiloxane precursor has a molar ratio of unhydrioyzable functional groups
  • any organic polysiloxane for the organic polysiloxane precursor, any organic polysiloxane
  • precursor containing silicon, oxygen, carbon, and hydrogen atoms can be used.
  • the organic polysiloxane precursor has one or more silane
  • R 1 is hydrogen, an aryl, a vinyl, an allyl, or a linear or branched Ci to C 4
  • R 2 is a linear or branched Ci to C 4 alkoxy
  • p is an integer of 1 or 2.
  • each of R 3 and R 5 is hydrogen, fluorine, an aryl, a vinyl, an allyl, or a
  • each of R 4 and R 6 is a linear or branched C-i to C 4 alkoxy
  • M is a Ci to C ⁇ alkylene or phenylene
  • each of q and r is an integer of 0 to 2.
  • R 7 is hydrogen, fluorine, an aryl, a vinyl, an allyl, or a linear or branched
  • Ci Ci to C 4 alkyl substituted by fluorine or unsubstituted
  • R 8 is hydrogen, a hydroxy, or a linear or branched Ci to C 4 alkoxy or
  • R 9 is fluorine, an aryl, a vinyl, an allyl, or a linear or branched Ci to C 4
  • R 10 is a linear or branched Ci to C 4 alkoxy
  • each of m and n is an integer of 3 to 7.
  • solvent or an ester based solvent is used.
  • ether based solvents such as ethylene glycol monomethyl
  • glycol dimethyl ether ethylene glycol diethyl ether, propylene glycol monomethyl
  • propylene glycol dimethyl ether propylene glycol diethyl ether, and propylene
  • glycol dipropyl ether glycol dipropyl ether
  • ester based solvents such as diethyl carbonate, methyl
  • propylene glycol diacetate may be used alone or in combination.
  • a non-alcoholic ether based solvent or a non-alcoholic ester Preferably, a non-alcoholic ether based solvent or a non-alcoholic ester
  • the organic solvent is comprised at 200 to 2000 parts by
  • organic solvent content is below 200 parts by weight, the coatability and the
  • water is used to hydrolyze the silane compound.
  • water is comprised in the coating composition.
  • water is selected from the coating composition.
  • the coating composition for insulating film production of the present invention is a coating composition for insulating film production of the present invention.
  • inventions may further comprise a pore generating material to obtain a uniform
  • a linear organic molecule or polymer preferably, a linear organic molecule or polymer, a cross-linked organic
  • dendrimer organic molecule or polymer may be used.
  • Preferable examples of the pore generating material are an aliphatic
  • the pore generating material has a
  • weight-average molecular weight ranging from 500 to 100,000
  • polystyrene-converted molecular weight and more preferably from 500 to
  • the pore generating material may comprise a silane compound to
  • generating material comprising a silane compound may be added in preparing
  • the pore generating material is comprised at 100 or less parts
  • the coating composition for insulating film production is prepared by a
  • the organic polysiloxane precursor is prepared by hydrolysis and
  • condensation by mixing a silane compound, an acid catalyst, and water, or a
  • any silane compound comprising silicon is any silane compound comprising silicon,
  • oxygen, carbon, and hydrogen atoms may be used.
  • one or more of the following groups may be used.
  • silane compounds selected from the group consisting of silane compounds
  • acid catalyst is not particularly limited.
  • hydrochloric acid nitric acid
  • nitric acid nitric acid
  • butanoic acid pentanoic acid, hexanoic acid, monochloroacetic acid,
  • the catalyst may be used alone or in combination,
  • the content of the catalyst may be determined according to the reaction
  • the organic polysiloxane precursor may be prepared from reaction in the
  • the organic solvent or from a combination of both.
  • water is comprised at 3 to 40 moles for 1 mole of the silane
  • silane compound or silane oligomer may be used.
  • silane compound or silane oligomer may be used.
  • aliphatic radicals Preferably, aliphatic radicals, branched radicals, and the like.
  • hydrocarbon based solvents such as n-pentane, /-pentane, n-hexane, /-hexane,
  • hydrocarbon based solvents such as benzene, toluene, xylene,
  • solvents such as acetone, methyl ethyl ketone, methyl-n-propyl ketone,
  • ether n-butyl ether, diglyme, dioxin, dimethyldioxin, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol-n-propyl ether, ethylene
  • glycol dimethyl ether ethylene glycol diethyl ether, propylene glycol monomethyl
  • propylene glycol dimethyl ether propylene glycol diethyl ether, and propylene
  • glycol dipropyl ether glycol dipropyl ether
  • ester based solvents such as diethyl carbonate, methyl
  • glycol diacetate and propylene glycol diacetate; or amide based solvents such
  • N-methylpyrrolidone formamide
  • N-methylformamide N-ethylformamide
  • N-ethylacetamide, N,N-dimethylacetamide, and N,N-diethylacetamide may be
  • organic polysiloxane precursor is not particularly limited.
  • the organic polysiloxane precursor is not particularly limited.
  • the organic polysiloxane precursor is not particularly limited.
  • the organic polysiloxane precursor is not particularly limited.
  • reaction is performed in a temperature range of 0 to 100TJ .
  • temperature may be kept constant during the reaction, or it may be controlled
  • Such low alcohol may impair coatability and mechanical strength of the insulating film.
  • an alcohol solvent having a high boiling point is
  • the alcohol content is as low as possible.
  • the resultant organic polysiloxane precursor comprises one or more
  • silane compounds selected from the group consisting of silane compounds
  • hydrolyzed and condensed repeating unit therefrom as a hydrolyzed and condensed repeating unit.
  • it has a
  • weight-average molecular weight ranging from 500 to 30,000.
  • present invention comprising the organic polysiloxane precursor, the organic
  • solvent used in preparing the organic polysiloxane precursor may be used as it
  • ether based solvents such as ethylene glycol monomethyl
  • glycol dimethyl ether ethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether,
  • propylene glycol dimethyl ether propylene glycol diethyl ether, and propylene
  • glycol dipropyl ether glycol dipropyl ether
  • ester based solvents such as diethyl carbonate, methyl
  • composition may further comprise a pore generating material to
  • a linear organic molecule or polymer a cross-linked organic
  • dendrimer organic molecule or polymer may be used.
  • the present invention provides a low dielectric insulating film for a
  • a silicon wafer For the substrate, a silicon wafer, an SiO 2 wafer, an SiN wafer, or a
  • the coating composition for insulating film production may be coated by
  • a common coating method Preferably, it may coated by spin coating, dip
  • spin coating is used when an interiayer insulating film for a
  • multi-layered circuit semiconductor device is prepared.
  • Thickness of the insulating film may be controlled by varying viscosity of
  • the insulating film has a thickness ranging from 0.05 to 2 ⁇ m.
  • a low dielectric insulating film having a three-dimensional structure may
  • drying is performed in the temperature range of 50 to 250 TJ .
  • hardening may proceed before sufficient drying, so that it is
  • baking is performed at a temperature of 300 TJ or
  • organic polysiloxane polymer is incomplete, so that the mechanical strength and
  • the drying and baking processes may be performed continuously while
  • Heating may be performed using a hot plate, oven, or
  • the heating method may be used to control the heating method in any order to control the heating method.
  • an oxygen-containing gas for example, air
  • in vacuum or in an ammonia- or hydrogen-containing gas atmosphere.
  • ammonia- or hydrogen-containing gas atmosphere for example, air
  • the present invention also provides such prepared insulating film and a
  • LSIs system LSIs
  • DRAMs DRAMs
  • SDRAMs SDRAMs
  • RDRAMs D-RDRAMs
  • capping layers hard mask layers, etch-stop layers, and so forth.
  • etch-stop layers hard mask layers, etch-stop layers, and so forth.
  • the coating composition for insulating film production of the present invention is a coating composition for insulating film production of the present invention.
  • reaction solution was diluted with diethyl ether solvent and
  • the resultant organic polysiloxane precursor had a
  • Pre-baking was performed on a hot plate at 80 TJ and 150TJ , respectively, for 1
  • the prepared insulating film had a dielectric constant of 2.98, elasticity
  • a coating composition for insulating film production was prepared in the
  • An insulating film was prepared as in Example 1 , except for adding 1.0 g
  • PEO polyethylene oxide
  • PPO polypropylene oxide
  • PEO polyethylene oxide
  • composition for insulating film production is a composition for insulating film production.
  • the prepared insulating film had a dielectric constant of 2.26, elasticity of
  • a coating composition for insulating film production was prepared in the
  • the prepared insulating film had a dielectric constant of 3.16, elasticity of
  • a coating composition for insulating film production was prepared in the
  • An insulating film was prepared as in Example 1 , except that 0.05 g of
  • the prepared insulating film had a dielectric constant of 3.14, elasticity of
  • reaction solution was diluted with diethyl ether solvent and washed with water until the pH became neutral. Magnesium sulfate was added
  • the resultant organic polysiloxane precursor had a
  • An insulating film was prepared as in Example 1 , except that 0.5 g of
  • the prepared insulating film had a dielectric constant of 3.10, elasticity of
  • a coating composition for insulating film production was prepared in the
  • An insulating film was prepared as in Example 2, except that water was
  • the prepared insulating film had a dielectric constant of 2.33, elasticity of 4.9 Gpa, and hardness of 0.60 GPa.
  • An insulating film was prepared as in Example 1 , except that 1.0 g of
  • the prepared insulating film had a dielectric constant of 2.21 , elasticity of
  • a coating composition for insulating film production was prepared in the
  • the prepared insulating film had a dielectric constant of 2.20, elasticity of
  • a coating composition for insulating film production was prepared in the
  • organic polysiloxane precursor had a weight-average
  • An insulating film was prepared as in Example 1, except for adding 3.0 g
  • the prepared insulating film had a dielectric constant of 2.49, elasticity of
  • a coating composition for insulating film production was prepared in the
  • a coating composition for insulating film production was prepared in the
  • the prepared insulating film had a dielectric constant of 2.48, elasticity of
  • a coating composition for insulating film production was prepared in the
  • An insulating film was prepared as in Example 1 , except for adding 0.3 g
  • PEO polyethylene oxide
  • PPO polypropylene oxide
  • PEO polyethylene oxide
  • composition for insulating film production is a composition for insulating film production.
  • the prepared insulating film had a dielectric constant of 2.33, elasticity
  • Al (aluminum) was deposited on the insulating film, and the dielectric constant
  • polysiloxane precursor having a small molecular weight and a specific amount of
  • Example 2 had a lower dielectric constant and better elasticity
  • the present invention provides a coating
  • composition for insulating film production having a low dielectric constant
  • a semiconductor device comprising the insulating film.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Computer Hardware Design (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Formation Of Insulating Films (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
EP04724894.3A 2003-04-09 2004-03-31 Beschichtungsmasse zur herstellung einer isolierfolie, deren verwendung zur herstellung einer isolierfolie, daraus hergestellte isolierfolie für halbleitervorrichtung sowie selbige enthaltende halbleitervorrichtung Expired - Lifetime EP1537183B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
KR2003022307 2003-04-09
KR20030022307 2003-04-09
PCT/KR2004/000747 WO2004090058A1 (en) 2003-04-09 2004-03-31 Coating composition for insulating film production, preparation method of insulation film by using the same, insulation film for semi-conductor device prepared therefrom, and semi-conductor device comprising the same

Publications (3)

Publication Number Publication Date
EP1537183A1 true EP1537183A1 (de) 2005-06-08
EP1537183A4 EP1537183A4 (de) 2007-08-08
EP1537183B1 EP1537183B1 (de) 2014-05-14

Family

ID=36674876

Family Applications (1)

Application Number Title Priority Date Filing Date
EP04724894.3A Expired - Lifetime EP1537183B1 (de) 2003-04-09 2004-03-31 Beschichtungsmasse zur herstellung einer isolierfolie, deren verwendung zur herstellung einer isolierfolie, daraus hergestellte isolierfolie für halbleitervorrichtung sowie selbige enthaltende halbleitervorrichtung

Country Status (7)

Country Link
US (2) US7345351B2 (de)
EP (1) EP1537183B1 (de)
JP (1) JP4409515B2 (de)
KR (1) KR100579855B1 (de)
CN (1) CN100457844C (de)
TW (1) TWI312801B (de)
WO (1) WO2004090058A1 (de)

Families Citing this family (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5128044B2 (ja) * 2003-12-10 2013-01-23 東京応化工業株式会社 シリコン基板又は金属配線パターンが設けられたシリコン基板被覆用シリカ系被膜形成用材料の製造方法
KR101119141B1 (ko) * 2005-01-20 2012-03-19 삼성코닝정밀소재 주식회사 폴리머 나노 입자를 포함하는 저유전 박막 형성용 조성물및 이를 이용한 저유전 박막의 제조방법
KR100824037B1 (ko) * 2005-03-16 2008-04-21 주식회사 엘지화학 절연막 형성용 기공형성제 조성물, 이를 포함하는 절연막형성용 조성물, 이를 이용한 절연막의 제조 방법, 및이로부터 제조되는 절연막
KR100775100B1 (ko) * 2005-03-16 2007-11-08 주식회사 엘지화학 절연막 형성용 조성물, 이로부터 제조되는 절연막, 및 이를포함하는 전기 또는 전자 소자
JP2007046010A (ja) * 2005-08-12 2007-02-22 Fujifilm Corp 膜形成用組成物、絶縁膜、およびその製造方法
JP2007070480A (ja) * 2005-09-07 2007-03-22 Fujifilm Corp 膜形成用組成物、絶縁膜およびその製造方法
KR101139052B1 (ko) * 2005-12-06 2012-04-30 삼성전자주식회사 불소를 포함하는 유기절연체 조성물 및 이를 이용한 유기박막 트랜지스터
US8197757B2 (en) * 2006-07-07 2012-06-12 Drexel University Electrical insulation of devices with thin layers
KR100955570B1 (ko) * 2006-09-18 2010-04-30 주식회사 엘지화학 저온 경화형 보호막 형성용 조성물, 이로부터 제조되는보호막, 및 이를 포함하는 기재
CN101535892A (zh) 2006-11-01 2009-09-16 皇家飞利浦电子股份有限公司 凹凸层和制作凹凸层的压印方法
TW200840554A (en) * 2007-02-28 2008-10-16 Alcon Inc Coated medical implants and lenses
US9353268B2 (en) 2009-04-30 2016-05-31 Enki Technology, Inc. Anti-reflective and anti-soiling coatings for self-cleaning properties
US20100275815A1 (en) * 2009-04-30 2010-11-04 Bakul Champaklal Dave Anti-Reflective and Anti-Soiling Coatings with Self-Cleaning Properties
US8864897B2 (en) 2009-04-30 2014-10-21 Enki Technology, Inc. Anti-reflective and anti-soiling coatings with self-cleaning properties
US9376593B2 (en) 2009-04-30 2016-06-28 Enki Technology, Inc. Multi-layer coatings
WO2011159854A1 (en) * 2010-06-17 2011-12-22 Janssen Pharmaceutica Nv Cyclohexyl-azetidinyl antagonists of ccr2
KR101887243B1 (ko) * 2011-07-13 2018-08-09 에이지씨 세이미 케미칼 가부시키가이샤 경화성 수지 조성물 및 그 용도
JP5637629B2 (ja) * 2011-07-22 2014-12-10 株式会社ジャパンディスプレイ 表示装置
JP6086739B2 (ja) * 2013-01-21 2017-03-01 東京応化工業株式会社 絶縁膜形成用組成物、絶縁膜の製造方法、及び絶縁膜
US8668960B1 (en) 2013-02-08 2014-03-11 Enki Technology, Inc. Flow coating apparatus and method of coating
US9382449B2 (en) 2014-09-19 2016-07-05 Enki Technology, Inc. Optical enhancing durable anti-reflective coating
US9598586B2 (en) 2014-07-14 2017-03-21 Enki Technology, Inc. Coating materials and methods for enhanced reliability
US9376589B2 (en) 2014-07-14 2016-06-28 Enki Technology, Inc. High gain durable anti-reflective coating with oblate voids
WO2016167892A1 (en) 2015-04-13 2016-10-20 Honeywell International Inc. Polysiloxane formulations and coatings for optoelectronic applications
KR20180013520A (ko) * 2016-07-29 2018-02-07 에스케이하이닉스 주식회사 미세 갭필용 중합체 및 이를 이용한 반도체 소자의 제조 방법
US10544330B2 (en) 2017-01-20 2020-01-28 Honeywell International Inc. Gap filling dielectric materials

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5496402A (en) * 1993-09-30 1996-03-05 Tokyo Ohka Kogyo Co, Ltd. Method and liquid coating composition for the formation of silica-based coating film on substrate surface
EP1090967A2 (de) * 1999-09-29 2001-04-11 JSR Corporation Beschichtungszusammensetzung für die Filmherstellung, Verfahren zur Filmherstellung und isolierende Filme
WO2001074957A1 (fr) * 2000-04-04 2001-10-11 Asahi Kasei Kabushiki Kaisha Composition de revetement pour la production de films minces d'isolation
US20010055891A1 (en) * 2000-04-28 2001-12-27 Min-Jin Ko Process for preparing insulating material having low dielectric constant

Family Cites Families (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2851871B2 (ja) 1989-07-21 1999-01-27 触媒化成工業株式会社 半導体装置およびその製造方法
JP2831398B2 (ja) 1989-09-28 1998-12-02 触媒化成工業株式会社 半導体装置の製造方法
JP2718231B2 (ja) * 1990-01-10 1998-02-25 三菱電機株式会社 高純度末端ヒドロキシフェニルラダーシロキサンプレポリマーの製造方法および高純度末端ヒドロキシフェニルラダーポリシロキサンの製造方法
JP3207929B2 (ja) * 1992-07-16 2001-09-10 東レ・ダウコーニング・シリコーン株式会社 半導体素子被覆剤および半導体装置
JPH08130247A (ja) 1994-10-31 1996-05-21 Nippon Zeon Co Ltd シロキサン系ポリマー含有塗布液及びその製造方法
JP4159124B2 (ja) 1997-03-19 2008-10-01 ダウ・コ−ニング・コ−ポレ−ション 導電性コーテイング材の製造方法
JP2000038509A (ja) 1998-05-18 2000-02-08 Jsr Corp 多孔質膜形成用組成物、該組成物の製造方法、膜の形成方法および多孔質膜
KR100618301B1 (ko) * 1998-09-01 2006-08-31 쇼꾸바이 카세이 고교 가부시키가이샤 낮은 유전상수를 지니는 실리카-포함 필름을 형성하기위한 코팅 액체 및 그의 필름으로 코팅된 기질
JP4228431B2 (ja) 1998-10-02 2009-02-25 日油株式会社 水分散性シリコーン組成物の製造方法
JP2001115021A (ja) 1999-10-18 2001-04-24 Asahi Kasei Corp シリカ前駆体/有機ポリマー組成物
JP2001237240A (ja) 2000-02-23 2001-08-31 Hitachi Chem Co Ltd 低誘電率膜及びこの低誘電率膜を有する半導体素子
US6759098B2 (en) * 2000-03-20 2004-07-06 Axcelis Technologies, Inc. Plasma curing of MSQ-based porous low-k film materials
JP2001279163A (ja) 2000-03-31 2001-10-10 Hitachi Chem Co Ltd シリカ系被膜形成用塗布液、シリカ系被膜の製造法、シリカ系被膜、これを用いた半導体素子及び多層配線板
JP4117441B2 (ja) 2000-04-10 2008-07-16 Jsr株式会社 膜形成用組成物の製造方法、膜形成用組成物、膜の形成方法およびシリカ系膜
JP2001308089A (ja) 2000-04-25 2001-11-02 Hitachi Chem Co Ltd 低誘電率膜及びこの低誘電率膜を有する半導体素子
JP2002038089A (ja) 2000-07-28 2002-02-06 Hitachi Chem Co Ltd シリカ系被膜及びそのシリカ系被膜を有する半導体装置
JP2002038091A (ja) 2000-07-28 2002-02-06 Hitachi Chem Co Ltd シリカ系被膜及びそのシリカ系被膜を有する半導体装置
JP2002201415A (ja) 2000-12-28 2002-07-19 Hitachi Chem Co Ltd シリカ系被膜形成用塗布液、シリカ系被膜の製造方法及び半導体装置
US6632748B2 (en) * 2001-03-27 2003-10-14 Samsung Electronics Co., Ltd. Composition for preparing substances having nano-pores
JP2002299441A (ja) * 2001-03-30 2002-10-11 Jsr Corp デュアルダマシン構造の形成方法
US6852367B2 (en) * 2001-11-20 2005-02-08 Shipley Company, L.L.C. Stable composition
US7091287B2 (en) * 2001-12-27 2006-08-15 Lg Chem, Ltd. Nanopore forming material for forming insulating film for semiconductors and low dielectric insulating film comprising the same
KR100515583B1 (ko) * 2002-06-27 2005-09-20 주식회사 엘지화학 유기실리케이트 중합체 및 이를 함유하는 절연막
KR20040018710A (ko) * 2002-08-26 2004-03-04 주식회사 엘지화학 유기실리케이트 중합체의 제조방법
JP2004277508A (ja) 2003-03-13 2004-10-07 Hitachi Chem Co Ltd シリカ系被膜形成用組成物、シリカ系被膜及びその形成方法並びにシリカ系被膜を備える電子部品

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5496402A (en) * 1993-09-30 1996-03-05 Tokyo Ohka Kogyo Co, Ltd. Method and liquid coating composition for the formation of silica-based coating film on substrate surface
EP1090967A2 (de) * 1999-09-29 2001-04-11 JSR Corporation Beschichtungszusammensetzung für die Filmherstellung, Verfahren zur Filmherstellung und isolierende Filme
WO2001074957A1 (fr) * 2000-04-04 2001-10-11 Asahi Kasei Kabushiki Kaisha Composition de revetement pour la production de films minces d'isolation
US20010055891A1 (en) * 2000-04-28 2001-12-27 Min-Jin Ko Process for preparing insulating material having low dielectric constant

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See also references of WO2004090058A1 *

Also Published As

Publication number Publication date
CN100457844C (zh) 2009-02-04
EP1537183B1 (de) 2014-05-14
US7345351B2 (en) 2008-03-18
US20080145677A1 (en) 2008-06-19
TW200506015A (en) 2005-02-16
JP2006516156A (ja) 2006-06-22
US20060045984A1 (en) 2006-03-02
TWI312801B (en) 2009-08-01
KR100579855B1 (ko) 2006-05-12
KR20040087888A (ko) 2004-10-15
CN1697865A (zh) 2005-11-16
EP1537183A4 (de) 2007-08-08
US7648894B2 (en) 2010-01-19
JP4409515B2 (ja) 2010-02-03
WO2004090058A1 (en) 2004-10-21

Similar Documents

Publication Publication Date Title
US7648894B2 (en) Coating composition for insulating film production, preparation method of insulation film by using the same, insulation film for semi-conductor device prepared therefrom, and semi-conductor device comprising the same
US6806161B2 (en) Process for preparing insulating material having low dielectric constant
EP1564269A1 (de) Zusammensetzung zur bildung eines porösenfilms, poröser film, verfahren zu seiner herstellung, zwischenschichtisolierfilm und halbleitervorrichtung
US7238627B2 (en) Organosilicate polymer and insulating film therefrom
EP1328571B1 (de) Verfahren zur herstellung von organischem silicatpolymer
US7834119B2 (en) Organic silicate polymer and insulation film comprising the same
JP4049775B2 (ja) 有機シリケート重合体およびこれを含む絶縁膜
KR100645682B1 (ko) 유기실록산 수지 및 이를 이용한 절연막
WO2004090019A1 (en) Organo-silsesquioxane polymers for forming low-k dielectrics
JP2004307693A (ja) 多孔質膜形成用組成物、多孔質膜の製造方法、多孔質膜、層間絶縁膜、及び半導体装置
JP2004269692A (ja) 多孔質膜形成用組成物、多孔質膜の製造方法、多孔質膜、層間絶縁膜、及び半導体装置
KR100826208B1 (ko) 유기실록산 중합체의 제조방법, 및 이를 이용한 절연막의제조방법
KR100508901B1 (ko) 유기실리케이트 중합체 및 이를 함유하는 절연막
KR100508902B1 (ko) 유기실리케이트 중합체 및 이를 함유하는 절연막
KR20040018710A (ko) 유기실리케이트 중합체의 제조방법
KR20030082692A (ko) 유기실리케이트 중합체 및 이를 함유하는 절연막

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20041220

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL LT LV MK

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: LG CHEM, LTD.

DAX Request for extension of the european patent (deleted)
RIN1 Information on inventor provided before grant (corrected)

Inventor name: KO, MIN-JIN

Inventor name: KANG, GWI-GWON

Inventor name: PARK, SANG-MIN

Inventor name: CHOI, BUM-GYU

Inventor name: KANG, JUNG-WON

Inventor name: KIM, BYUNG-RO

Inventor name: NAM, HYE-YEONG, LG CHEM LTD.

Inventor name: MOON, MYUNG-SUN

Inventor name: KIM, YOUNG-DUK

A4 Supplementary search report drawn up and despatched

Effective date: 20070711

17Q First examination report despatched

Effective date: 20071130

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

INTG Intention to grant announced

Effective date: 20140321

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 668321

Country of ref document: AT

Kind code of ref document: T

Effective date: 20140615

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602004045097

Country of ref document: DE

Effective date: 20140626

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 668321

Country of ref document: AT

Kind code of ref document: T

Effective date: 20140514

Ref country code: NL

Ref legal event code: VDEP

Effective date: 20140514

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140514

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140815

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140514

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140514

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140514

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140514

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140514

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140915

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140514

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140514

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140514

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140514

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140514

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140514

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602004045097

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140514

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20150217

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140514

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602004045097

Country of ref document: DE

Effective date: 20150217

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140514

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20150331

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140514

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150331

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150331

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20150331

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 13

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 14

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20040331

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140514

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140514

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 15

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20230221

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20230220

Year of fee payment: 20

Ref country code: DE

Payment date: 20230220

Year of fee payment: 20

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 602004045097

Country of ref document: DE

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

Expiry date: 20240330

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20240330